Halogeno-thiophene-1, 1-dioxides



Unitfid States Patent HALOGENO-THIOPHENE-LI-DIOXIDES Henry Bluestone, University Heights, Ohio,, assign'or to Diamond Alkali Company, Cleveland, 01110,, a. corporation of Delaware No: Drawing. Filed Jan. 17,1958, SertNo', 709,414!) 5 Claims. (Cl; 260-3321) This invention relates to novel compounds represented by the structure Xr-CCXs wherein X X X and X, are selected from the group consisting of hydrogen and halogen atoms, e.g., fluorine, chlorine, bromine, or iodine, chlorine being preferred, at least one X being halogen, to their preparation, to the application of such compounds, and certain polyhalo intermediates.

More specifically, the presently preferred compounds of this invention may be represented by the structure wherein X is a halogen atom, chlorine being preferred, and at least one X being halogen.

Specific illustrative compounds falling within the scope of this invention are:

3,4-dichlorothiophene 1,l-dioxide.. 3-chlorothiophene 1,1-dioxide. 3,4-dibromothiphene 1,1-dioxide. 3-bromothiophene 1,1-dioxide. 2,3-dichlorothiophene 1,1-dioxide. 2,5'-dichlorothiophene 1,1-dioxide. 2,4-dichlorothiophene 1,1-dioxide. 3,4-difl-uorothiophene 1,1-dioxide. 2,3,4,S-tetrachlorothiophene 1,1-dioxide. 2,3,4-tribromothiophene 1,1-dioxide. 2,3,4-trichlorothiophene 1,1-dioxide. 2,5-dibromothiophene 1,1-dioxide.

with an alkaline reagent, wherein X X X X X and X,;- are selected from the group consisting of hydrogen and halogen, at least X X and one other X being halogen, whereby two moles of HX are eliminated.

'Alternately, compounds of this invention may b'e'prepared by dehydrohalogenatinga compound of the struc'- ture wherein X X X X and X, are selected from the group consisting of hydrogen and halogen, at least X and one other X being halogen, whereby one mole of HX is eliminated, with an alkaline reagent.

More specifically, compounds of this invention may be; prepared by chemically reacting a compound of the struc-* ture.

with an alkaline reagent, e.g., an alkali metal hydroxide I such as sodium hydroxide or potassium hydroxidq' ammonia, ammonium hydroxide or an alkali metal carbonate.

such as sodium carbonate, potassium carbonate, sodium:

bicarbonate or an amine such as diethylamine, ethanolamine, or pyridine, Where X is a halogen atom, .e.g.,

fluorine, chlorine, bromine, or iodine, chlorine being pre-' ferred.

Typically the above reactions may be carried .outin the presence of a solvent, e.g, an organic solvent such methanol, ethanol, acetone, cyclohexanone, xylene, or water. ture high enough to cause chemical, reaction, e.g.,,from. 0 C. up to the decomposition temperature of the start-- ing materials, although desirably below C., preferably'within the range from 20-35 C.

Exemplary of the above preparations, a halothiophene lgl-dioxide may be prepared by chemically reacting a polyhalotetrahydrothiophene 1,1-dioxide, such as 3,3,4;4 tetrachlorotetrahydrothiophene 1,1-dioxide, 2,3,4,4"-tetrachlorotetrahydro thiophene 1,1-dioxide, 2,3,3,4-tetrachlorotetrahydrothiophene l,l-dioxide, 3,4-dichloro 3,4=di--- fluorotetrahydrothiophene 1,1-dioxide, 2,3,4-tribromotetra-- hydrothiophene 1,1-dioxide, 2,3,3,4,4-pentachlorotetrahydrothiophene 1,1-dioxide, 3,4-dibromo-3,4-dichlorotetra V hydrothiophene 1,1-dioxide, 3,3,4-trichloro-4-fiuorotetrax hydrothiophene 1,1-dioxide or a polyhalodihydrothiophene 1,1-dioxide, such as 2,3,4,4-tetrahalodihydrothi0 phene 1,1-dioxide, 3,3,4,5-tetrahalodihydrothiophene, Lit t. dioxide, 3,3,4-trihalodihydrothiophene 1,1-dioxide, 2,334) g j tr r 2,976,291 Ce Patented Mar, 21,1196;

The reactions are also carried out at a temperatrihalodihydrothiophene 1,1-dioxide, i.e., 3,3,4,5-tetrachlorodihydrothiophene 1,1-dioxide, 2,3,4,4-tetrachlorodihydrothiophene 1,1-dioxide, 2,3,4-tribromodihydrothiophene 1,1-dioxide, 3,4-dichloro-4-fluorodihydrothiophene 1,1-dioxide, 3,3,4-tribromodihydrothiophene 1,1-dioxide with an alkaline reagent, as previously defined; also a solvent may be used to advantage, e.g., an organic solvent such as methanol, ethanol, propanol, acetone, cyclohexanone, xylene, or water. The reaction is carried out at a temperature high enough to cause chemical reaction, e.g., from C. up to the decomposition temperature of the starting materials, although desirably below 115 C.,'

preferably Within the range from 2035 C.

Recovery of the product may be carried out by adding a miscible solvent in which the product is relatively insoluble, to the reaction mixture until the product precipitates, or the original solvent may be removed through distillation, preferably at reduced pressure.

The novel compounds of this invention are useful as chemical intermediates and exhibit a high degree of chemical reactivity; also these novel compounds possess marked biological activity. More specifically, these compounds are active pesticides, e.g., insecticides, as for the control of aphids; fungicides, as for the control of soil fungi; herbicides, as in the control of undesirable plant growth; and for the control of microorganism growth, e.g., bactericides.

These compounds may be used alone or in combination with other known biologically active materials, such as other polyhydrothiophene 1,1-dioxides, organic phosphate pesticides, chlorinated hydrocarbon insecticides, foliage and soil fungicides, preand post-emergent herbicides, and the like.

While compounds of this invention may be employed in a variety of applications, biologically active or otherwise, when employed as biologically active materials, it will be understood, of course, that such compounds may be utilized in diverse formulations, both liquid and solid, including finely-divided powders and granular materials as well as liquids such as solutions, concentrates, emulsifiable concentrates, slurries and the like, depending upon the application intended and the formulation media desired.

Thus, it will be appreciated that compounds of this invention may be employed to form biologically active substances containing such compounds as essential active ingredients thereof, which compositions may also contain carriers, including finely-divided dry or liquid diluents, extenders, fillers, conditioners, including various clays, diatamaceous earth, talc, spent catalyst, aluminasilica material, solvents, diluents, etc., including water and various organic liquids, such as benzene, toluene, chlorinated benzene, acetone, cyclohexanone, xylene, carbon disulfide and various mixtures thereof.

When liquid formulations are employed or dry materials prepared which are to be used in liquid form, it is desirable in certain instances additionally to employ a wetting, emulsifying or dispersing agent to facilitate use .of the formulation, e.g., anionic and cationic surface active agents, cationic quaternary ammonium salt, alkyl aryl sulfonate surface active agents, non-ionic polyoxyalkylene fatty ester surface active agents, Triton X-155 (alkyl aryl polyether alcohol, US. Patent No. 2,504,064). A detailed list of such agents is set forth in an article by John W. McCutcheon in Soap and Chemical Specialities, vol. 31, No. 7-10, 1955. In general, less than 10% by weight of the surface active agents is present in the compositions of the invention and usually less than 1% by weight is present.

The term carrier employed in the specification and claims is intended to refer broadly to materials constituting a major proportion of a biologically active or other formulation and hence includes finely-divided materials,

amaze? both liquid and solid as aforementioned conveniently used in such application.

In order that those skilled in the art may more completely understand the present invention and the preferred methods by which the same may be carried into efiect, the following specific examples are offered.

EXAMPLE I Preparation of 3,4-dichlorothiophene LI-dioxide 258 g. (1.0 mol) of 3,3,4,4-tetrachlorotetrahydrothiophene 1,1-dioxide is dissolved in 2 liters of methanol at room temperature. Aqueous ammonia (28%) (approximately 150 g.) is added portionwise to the methanol solution with stirring until the solution remains basic. The solution is cooled during the addition to maintain 'a temperature of 3035 C. The solution is allowed to stand to insure complete reaction, enough aqueous ammonia being added to maintain a basic solution.

One liter of distilled water is then added to the methanol solution and the methanol is distilled olfat 20-25 mm. Hg pressure employing a water bath at about 40 C. The precipitated product is filtered off and washed with distilled water. After recrystallization, the product is dried in an evacuated desiccator yielding the desired C H Cl- O S, which melts with decomposition at 112-113 C. Preparation of the desired product is in dicated by the following eleme'ntal analyses:

Actual, Calculated, Element Percent Percent y ety et.

O 25. 91 25. 96 PI 38. 0 38. 32

This 3,4-dichlorothiophene 1,1-dioxide is greater than 5% soluble in acetone, cyclohexanone and xylene but less than 5% soluble in water.

EXAMPLE II product of Example I at the above concentration, 100% 5 mortality is observed.

EXAMPLE III 25 houseflies, 4 to 5 days old, are caged over small paper cups containing a piece of cellu-cotton impregnated with 15 ml. of test formulation and 10% concentration of sugar. The test formulations comprise 2000 p.p.m.

and 1000 p.p.m. of the product of Example I, 5% acetone, 0.01% Triton X-155, balance water. Mortality counts taken 24 hours after application show greater than and greater than 60% mortality, respectively, at the above concentrations.

EXAMPLE IV Further insecticidal utility is shown using the bean aphid, Aphis fabae, cultured on Nasturtium plants. No attempt is made to select insects of a given age in this test. Nasturtium plants are infested with approximately aphids and are treated by pouring a formulation (2000 p.p.m, product of Example I, 5% acetone, 0.01%

Triton X-l55, balance water) on the soil at a rate equivalent to 64 lbs/acre. Aphid mortality of 100% is obs served 24 hours after treatment for the 3,4-dich1orothiophene 1,1-dioxide.

EXAMPLE .V

Spore gqrminan tests on glass slides are conducted via the test'tube dilution method adopted from the procedure recommended by the Americal Bhytopathological Societys committee on standardization of fungicidal tests. In this procedure, the product of Example I, in aqueous formulations at concentrations of 1000, 100. 1 and 1.0 parts per million, is tested for its ability to inhibit germination of spores from 7 to 10 day old cultures or Alternaria oleracea and Mon ilin z 'a fructicbliL 'Ih ese concentrations refer to initial concentrations before diluting 4 volumes with 1 volume of spore stimulant and spore suspension. Germination records are taken after 20 hours of incubation at 22 C. by counting 100 spores.

Results indicate that concentrations of less than 1.0 p.p.m. afiord disease control for both of the A. olerr zcea and M. Fructicola.

EXAMPLE VI Further fungicidal activity is demonstrated by the ability of 3,4-dichlorothiophene 1,1-dioxide to protect pea seed and seedlings from seed decay and damping 01f fungi (Pythiurn and Fusarium). In this test, infested soil in 4" x 4" x 3" plant band boxes is treated' by soil drench methods at rates equivalent to 16, 8,and 4 lbs/acre. Treatment is accomplished by pouring 70 ml. of the test formulation (concentration product of Example I, 5% acetone, 0.01% Triton Xl5 5, balance water) on .the surface of the soil. This is allowed'to stand until the next day when the soil is removed from each box and thoroughly mixed beforebeing replaced in the box. Three days after such treatment, 25 pea seeds, variety Perfection, are planted to a uniform "depth in each box. Percentage stands recorded 14 days after planting show 94%, 96% and 100% stands, respectively, at the above concentrations whereas the untreated soil control shows only a 3% stand, thus indicating high soil fungicidal activity.

EXAMPLE VII dishes containing filter paper discs moistened with-5 ml..

of the test formulation at each concentration. After 7. to days, the concentration of the test compound that inhibits germination of half of the seeds (ED. 50 values) the test crop is-determined. Accordingly, 3,4-dichlorothiophene |1,1-dioxide has an ED. 50 value between 10 and 100 p.p.m. for both radish and rye grass seeds.

EXAMPLE VIII Further to evaluate the efiects of the product of Example I upon the germination of seeds in soil, a mixture of seeds of six crop plants is broadcast in 8 x 8" x 2" metal cake pans filled to within /2" of the top with composted greenhouse soil. The seed is uniformly covered with about A of soil and watered. Twenty-four hours after such treatment, 80 ml. of an aqueous test formulation containing320 mg. of the product of Example I is sprayed at 10 lbs. air pressure uniformly over the surface of the pan. This treatment is equivalent to 64 lbs/acre. Additional evaluations are carried out at concentrations of 8 lbs/acre and 4 lbs/acre.

.6 The seed mixture contains representatives ofthree broad leafs: .t'u'rnip, flax, and alfalfa; and or jthr'jeegiasses; what,'millet and rye gras Two weeks after treatrii' t, recordsare taken on seedling stand as compared to t5 untreated control. 'U'sing' this procedure, data on teena W1 il i i T le Ta lirle I Results Indicate seams. Sana;

W 1? l l s ee s seem and r w- EXAMPLE IX To .test post emergence herbicidal activity, tomato plants, variety Bonny Best, 5 to 7 inches tall; corn,'va riety Cornell M- l (field corn) 4 to 6 inches tall; bean, yariety Tendergreen, just as the trofoliant leaves are ginning to unfold; and oats, yariety Clinton, 3 to 5 inches tall, are sprayed with an aqueous test formulatioin (3200 ppm.- product of Example I, 5% acetone, 0,01% Triton X-155, balance water) the plants are i with 100 ml. at lbs. air pressure while rotated on a turn table in a spray hood. Records are. 1 taken 14, days after treatment and herbicidal activityfisl a e 9 $3 m f fo no inju y to 11 f P 3. l Usin 1 2 t ge l'u e. 3.4-. i o hi p ene dioxide receives ratings as shown in Table II hereinbelow:

Table II 1 40 w PLANTS Concentration used in 1 Tomato Bean Corn Oats 3, 2tib.'-' -Q--- 11 11 10 1 Leon 11 9 s r .q

' See Example for explanation of procedure.

EXAMPLE x To detect root absorption and translocation in growing plants, tomato plants, variety Bonny Best, 5 to 7 inches tall, and corn plants, variety Cornell M-l, (field corn) 4 to 6 inches tall are treated by pouring] 5 1 in].

of a formulation consisting of 1000 ppm. test chemical,

5% acetone, 0.01 Triton X155, balance watenbn the soil of 4" pots in which the plants are growing. The test chemical is applied at the rate equivalent 7 .32 lbs; /acre Plants are held under control greenhouse I 7 conditions for 10'days before examination, at which time herbicidal effect is observed and ratings given based a scale from 0 for no injury to -1,1 for plant kill. "Using this procedure, the product I of Example I receivesa rating of for the tomato and 8 11)? the bean plantsl EXAMPLE x1 To evaluate bactericidal activity, the products of,

Example I is mixed withdistilled water containing 5%. 1

acetone: and 0.01% Triton X- 155 at a concentration'qf .1 256 {rpm Five ml. of the test formulation is'putinI each of four test tubes, to each of which-is then added one of the organisms Erwerzia amylovp ra, Xqn'thamon as' phas'eoli, Staphylococcus aureus, and Escher! h" the form of a saline solution of a bacterial suspension from potato dextrose agar plates. The tubes are then incubated for four hours at 30 C. after which transfers are made to sterile broth with a standard 4 ml. loop. The thus-inoculated broth is incubated for 48 hours at 37 C. at which time bacterial growth is rated on a percentage scale wherein =no growth. Using this procedure, the product of Example I receives ratings of 0, 0, 0, and 0 for each of the above organisms.

EXAMPLE XII In order to make an in vitro evaluation of the product of Example I as a nematode contact poison, nonplant parasitic nematodes, Panagrellus redivivus, are exposed by contact to the test chemical in small watch glasses (27 mm. diameter by 8 mm. deep), and placed in a 9 centimeter petri dish. Aqueous test formulations (1000 p.p.m. and 500 ppm. product of Example I, acetone, 0.01% Triton X-155, balance water) are added to the nematodes. Results are recorded 24 hours after treatment and from these, mortality ratings of 100% and 100%, respectively, are indicated for the above concentrations.

EXAMPLE XIII Outstanding ability of the 3,4-dichlorothiophene 1,1- dioxide as a fumigant nematode poison is demonstrated by exposing non-plant parasitic nematodes, Panagrellus redivivus, to the vapor of the test chemical in small watch glasses (27 mm. diameter by 8 mm. deep) in a 9 centimeter petri dish. Test formulations containing two and one mg. of the product of Example I, with 5% acetone, 0.01% Triton X-155, balance water, are used in the small watch glasses but not in contact with the nematodes. Observations after 24 hours indicate 100% and 100% mortality, respectively, using 3,4-dichlorothiophene 1,1- dioxide at the above concentrations.

EXAMPLE XIV Preparation of 2,4-dichlorothiophene 1,1-dioxide 5.16 g. (0.02 mol) of 2,3,4,4-tetrachlorotetrahydrothiophene 1,1-dioxide is dissolved in 20 ml. of methanol and the solution cooled in an ice bath. 2,85 g. of concentrated NH OH (0.06 mol of NH in water) is added portionwise. A precipitate of NH C1 forms; however,

upon addition of 250 ml. of water the NH Cl precipitate dissolves and the desired product precipitates as an oil. The mixture is extracted and crystallized with chloroform, benzene, and petroleum ether yielding the desired C H Cl O S.

EXAMPLE XV Preparation of 2,3,4-trichlorothiophene 1,1-di0xide 5.1 g. (0.02 mol) of 2,3,4,4-tetrachloro-2,3-dihydrothiophene 1,1-dioxide is dissolved in 50 ml. of methanol. 2.0 ml. of 28% NH in water is added and the solution allowed to stand for about 15-24 hours. Upon diluting with 500 ml. of water the desired product precipitates out as an oil. Upon extraction and recrystallization using chloroform, carbon tetrachloride, petroleum ether, benzene, and cyclohexane, the desired C HCl O S is ob-. tained having ultra violet spectrum peaks at 238 mp and 1,1-dioxide; 4-chloro-2,3-dihydrothiophene 1,1-dioxide;

tetrahydrothiophene 1,1-dioxide; and 3,4-dihydrothiophene 1,1-dioxide.

Table III BIOLOGICAL ACTIVITY Concentration which Atfords at Least Disease Control of the A. Oleracea and AI. Compound Structure Compound Name Fructtcola A. M. Oleracea Fructicola P.p.m. P.p.m. Cl-0-C-Cl 3,4-dichlorothiophene 1 1 I] 1,1-dloxide. H-C C-H S l/ \i O 0 1'1 ClCC-CI 3,4-dlchloro-2.3-di- 10-100 10-100 II I hydrothiophene O CH: 1,1-dioxide.

S 1! \t O 0 1'1 H ClC-( J-Cl 3,44ilchlorotetra 1, 000 1, 000

hydrothiophene 11,0 H; 1,1-dioxide.

B l! 0 0 1i! H-C--C-Cl 4-ch]oro-2,3-dihydro- 100-1, 000 100-1, 000

thiophene 1,1- H-C H: dioxide.

H 0 C H, Tetrahydrothiophene 1, 000 1, 000

1,1-dioxtde. H: CH: S t! \l 0 0 HC=CH 3,4-dlhydrothlophene IOU-1,000 1,000

(B (l: 1,1-dioxide. Ha H:

S t! \i 0 O dichlorothiophene 1,1-dioxide; 3,4-dichloro 2,3-dihydro1i thiophene 1,1-dioxide; 3,4'dichlorotetrahydrothiophene For test procedure and conditions see Example V.

It is to be understood that although the invention has been described with specific reference to particular embodiments thereof, it is not to be so limited, since chauges' and alterations therein may be made which are within the full intended scope of this invention as defined by the appended claims.

What is claimed is:

1. Compounds represented by the structure wherein is halogen.

' 9 3. 2,4-dichlorothiophene 1,1-dioxide. FOREIGN PATENTS 4. 3,4-dich1orothiophene 1,1-dioxide. 5. 2,3,4-trichlorothiophene 1,1-dioxide. 566930 Great Bmam 1945 OTHER REFERENCES References Cited in the file of this patent Backer et a1.: Rec. des Trav. Chim., v01. 53 (1934 UNITED STATES PATENTS 11527- Backer et al.: Rec. des Trav. Chim., v01. 56 (1937), 2,357,344 Morris Sept. 5, 1944 1 2, 4 2,377,626 Guy J 1945 Backer et a1.: Rec. des Trav. Chim., vol. 61 (1942), 2,439,345 Morris Apr. 6, 1948 786, 2,460,233 Morris J 1949 Wagner-Zook: Synthetic Organic Chemistry, Wiley, pp. 2,461,340 Morris Feb. 8, 1949 -3 1953), 7 2,653, Kosmin er 11 p 29, 1953 w. J. Bailey 612 211.: I. Am. Chem. Soc., V01. 76 (1954 2,691,616 Dickey et a1 t- 1 pp. 1932-1934. 2,758,955 Johnson et a1. Aug. 14, 1956 15 W. I. Bailey et -al.: J. Am. Chem. 800., vol. 76, pp.

2,799,616 Johnson Iu1y16, 1951 1934-1935 1954 

1. COMPOUNDS REPRESENTED BY THE STRUCTURE 